7-nitroso-7, 14-diazadispiro-[5.1.5.2]-pentadecane-15-thione and lower alkyl detrivatives thereof



United States Patent 7 NlTROS0-7,14-DIAZADISPIRO [5.1.5.2] PENTA- DECANE-lS-THIONE AND LOWER ALKYL DE- RIVATIVES THEREOF Wendell S. Cook, Fulton, Ohio, assignor to The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio No Drawing. Filed Aug. 11, 1964, Ser. No. 388,943

2 Claims. (Cl. 260-3093) This application is a continuation-in-part of Oberster and Cook Serial No. 163,896 filed January 2, 1962, now US. Patent 3,205,194.

This invention relates to 7-nitroso derivatives of imidazolidine thiones and their use as stabilizers for polymers and their vulcanizates. It includes the stabilized polymers and vulcanizates.

Various derivatives of imidazolidine 4 thiones are known in the literature.

The 7-nitroso derivatives of 7,14-diazadispiro-[5.15.2]- pentadecane-lS-thione and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups are stabilizers of diene elastomer emulsion polymers (for example, BR, SBR, NBR, ABR and IR) and their vulcanizates. Such alkyl derivatives are prepared from lower alkyl derivatives of the parent compound, by the procedure set forth in Example 1. The polymers and their vulcanizates are prepared in any usual manner, and the stabilizer is added at a convenient stage, preferably just prior to coagulation of the polymer or polymers.

The stabilizers of this invention include the 7-nitroso derivatives of the following which are illustrative:

3,1 1-dimethy1-7,14-diazadispiro- [5.1.5 .2]-pentadecanel5-thione 3,1 1-di-t-butyl-7,14-diazadispir0-[5. 1.5.2] -pentadecane- -thione 3,11-di-t-amyl-7,14-diazaclispiro-[5.1.5.21-pentadecane- 15 -thione 3, 1 1-di-n-butyl-7,14-diazadispiro- [5.1 .5.2] -pentadecanel5-thione 2,10-dimethyl-7,14-diazadispiro-[5.1.5.2]-pentadecane- 15-thione 2,10-di-n-butyl-7,14-diazadispiro-[5.1.5.2]-pentadecane- 15 -thione 2,10-di-t-octyl-7,l4-diazadispiro- [5.1.5.2]-pentadecane- 15 -thione 3,11-dicyclohexyl-7,14-diazadispiro-[5.1.5.2]-pentadecane- 1 S-thione 3,1l-diisopropyl-7,14-diazadispiro-[5.1.5.2]-pentadecane 15-thione 2,10-diethyl-7,14-diazadispiro-[5.1.5.2]-pentadecane-15- thione 2,4,10,12-tetramethyl-7,14-diazadispiro-[5.1.5.21-pentadecane- 1 S-thione 2,3,10,11-tetraethyl-17,14-diazadispiro-[5.1.5.2]-pentadecane- 1 S-thione The following examples illustrate more particularly the preparation of 7- and 14-nitroso-7,14-diazadispiro- [5.1.5.2]-pentadecane-15-thiones and their use in SBR. The 7-nitroso derivative can be used as a stabilizer in SBR and the other polymer rubbers referred to herein and their vulcanizates. The 7-nitroso derivatives of the See lower alkyl derivatives to which reference has been made are useful as stabilizers in all of these polymers and vulcanizates. The 14-nitroso derivatives are not suitable for use as stabilizers. The 7-nitroso derivatives are nonstaining and polymers containing them age with substantially no discoloration.

The parent compound, 7,l4-diazadispiro-[S.1.5.2]-pentadecane-lS-thione has the following formula:

The following examples illustrate the preparation of the 7- and 14-nitroso derivatives:

Example 1.7-nizr0s0 derivative of 7,14-diazazlispir0- [5 .1 .5 .2 -pentadecane-1 5-thz'0rze A solution of 23.8 grams of the parent compound in 1000 ml. of glacial acetic acid was prepared by heating the mixture to about C. The solution was cooled to room temperature and filtered to remove a slight amount of insoluble material. The solution was then stirred slowly and 9.6 grams of sodium nitrite was added over a period of about one hour. At the end of the addition, a thick crystal mass had formed in the flask. The product was collected on a filter and washed with cold water. The product was air dried. It weighed 24.3 grams and melted at 208-211 C.

Analysis.-Calcd for C H N SO: C58.40; H7.92; S11.99. Found: C58.93; H7.82; S11.96.

Example 2.14-nitr0so derivative 0 7,14-diazadispir0- [5.1.5.21-pentadecane-15-thione A solution of 11.9 grams of the parent compound in 500 ml. of glacial acetic acid was prepared by heating the mixture to about 60 C. To this warm solution was added 13 ml. of concentrated hydrochloric acid. Some material precipitated out at this point. Seven grams of sodium nitrite was added in small portions over a one hour period. The reaction mixture was then left at room temperature for several hours with occasional stirring. The reaction mixture was filtered and the product air dried. Eleven and one-half grams of product was obtained and melted with vigorous decomposition at 206 210 C. A mixed melting point with the product obtained in Example 1 (MP. 208211 C.) resulted in a lowering of the melting point to 197214 C.

Analysis.-Calcd for C H N SO: C58.40; H 7.92; 8-11.99. Found: C-58.97; H7.92; 8-11.94.

The position of the nitroso group in the isomeric compounds described in Examples 1 and 2 above 'was established using nuclear magnetic resonance spectral data.

In the following tables comparison has been made with a widely used commercial stabilizer for SBR polymer which is identified as Stabilizer I, and 7- and 14-nitnoso 3 derivatives of the parent compound were tested and compared With the parent compound, these latter stabilizers being identified in the following tables as Stabilizer A=7-nitroso derivative of 7,14-diazadispiro- [5.1.5.2]-pentadecane-l5-thione.

Stabilizer B=14-nitroso derivative of 7,14-diazadispiro- [5.1.5.2]-pentadecane-15-thione.

Stabilizer C=The parent compound of 7,14-diazadispiro- [5.1.5.2]-pentadecane-l5-thione.

In the tests 1.25 parts of Stabilizer I per 100 parts of SBR were employed, and for the i'midazolidine thione stabilizers only 0.5 part per 100 parts of SBR. The stabilizers were added to the SBR latexes prior to coagulation.

In Table I, the effects of oven aging SBR polymer containing stabilizers of this invention and the commercial stabilizer are compared before and after aging four days in an air circulating oven at 70 C.

TABLE I.POLYME R STABILIZATION Surface Rating Mooney Viscosity Orig. 4 Days Orig. 4 Days Polymer-l-Stabilizer A OK K 53.0 49. 5 Po1ymer+Stabilizer B 52. 5 P01ymer+Stabilizer C OK 53. 5 55. 5 P01ymer+Stabilizer I OK OK 48. 49. 0

1 Resinified.

Vm =Mooney at minimum viscosity Ts( Vm+1)=Time to start of cure which is the time in minutes required for increase in the Mooney of the stock from minimum viscosity to 1 Mooney unit above minimum viscosity.

T c(Vm+lO)=Time to substantial cure which is the time in minutes required for increase in the Mooney of the stock from minimum viscosity to 10 Mooney units above minimum viscosity.

TABLE II A I O Polymer-l-Stabilizer A Polymer+Stabilizer I 100 Polyn1er+Stabilizer C. .1 100 HA Blac 50 50 50 Oil 8 8 8 Stearie Ae1d 1. 5 1. 5 1.5 Zinc Oxide 3. 0 3. 0 3. 0 10 Accelerator 1.0 1.0 1.0 Sulfur I 1.75 1. 75 1. 7

Total 165. 165. 25 165. 25

Normal Stress-Strain:

300% Modulus, p.s.i 2,125 2, 200 2, 000 Tensile, p.s.i 3, 200 2, 250 3, 050 5 Elongation, percent 410 410 410 Aged 2 Days at 212 F.Oven

200% Modulus, p.s.i 2, 525 Tensile, p.s.i 2, 750 2, 575 2, 500 Elongation, percent 210 190 190 Aged 5 Hrs. at 260 F.Air Bomb:

200% Modulus, p.s.i 2 Tensile, p.s.i I 1, 100 825 650 Elongation, percent 120 80 70 Mooney Scorch at 275 Ts (Vm+1) 24. 5 22. 5 17.5 To (Vm+10) 29. 5 30.5 22.5 In 19. 75 19. 0 20. 75

25 The results show that the 7-nitroso derivative has ex- References Cited by the Examiner UNITED STATES PATENTS 2,806,036 9/1957 Christian 260-3097 2,899,442 8/1959 Hughes 260309.7 2,985,663 5/1961 Cormack et al 260-3097 2,992,205 7/1961 Broyles et a1 26045.8 3,003,995 10/1961 Schule 260-458 WALTER A. MODANCE, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

M. J. WELSH, N. TROUSOF, Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,275,650 September 27, 1966 Wendell 5. Cook It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the heading to the printed specification, line 5, for

"Fulton, Ohio" read Canal Fulton, Ohio column 1, line 46, for "2,10-di-t-octy1" read 2,10-di-tt-octy1 line 56, for "2,3,lO,11tetraethyl-l7" read 2,3,10,1l-tetraethyl-7 column 4, TABLE II, fourth column, line 9 thereof, for 1.7" read 1.75

Signed and sealed this 29th day of August 1967.

Attest:

ERNEST W. SWIDER EDWARD J BRENNER Attesting Officer Commissioner of Patents 

1. 7 - NITROSO-7,14-DIAZADISPIRO- 5.1.5.2!-PENTADECANE15-THIONE AND LOWER ALKYL DERIVATIVES THEREOF SUBSTITUTED ON METHYLENE GROUPS WHICH ARE CONNECTED TO TWO OTHER METHYLENE GROUPS. 